Restructuring hollow Au–Ag nanostructures for improved SERS activity

Hollow Au–Ag nanostructures with improved SERS performance were prepared by using a modified galvanic replacement reaction. The plasmon characteristics of the hollow structures are found to be highly sensitive to the volume of cathode, whether or not a co-reductant was used in the synthesis. It is found that the presence of a co-reductant viz., ascorbic acid (AA) during the reaction make the hollow structures capable to maintain its physical structure even after addition of excess cathode and also it transformes sacrificial templates into highly efficient hollow Au–Ag SERS substrates. In the galvanic replacement reaction conducted in presence of AA, where on one side the removal of Ag atoms make cavities to occur and on the other side a coating on the surface with Au and Ag atoms due to co-reduction take place simultaneously. Morphological observations indicated that it is possible to control the competition between these two mechanisms and to make Au–Ag hollow structures in tune with applications by optimizing the volume of cathode or AA. The SERS activity of these substrates were tested with crystal violet molecule as probe, using two different laser lines, 514 and 784.8 nm. In this report, the enhancement observed for hollow structures fabricated under optimum conditions are in the order of 10⁶. SERS measurements have shown that for a specific volume of cathode, substrates fabricated in presence of AA are superior to the other type and also the increase in enhancement factor is ∼10 fold. (paper)